Detergent sulphonic acid and sulphate salts of certain amphoteric detergents



United States Patent DETERGENT SULPHONIC ACID AND SUL- PHATE SALTS OF CERTAIN AMPHOTERIC DETERGENTS Hans S. Mannheirner, New York, N. Y.

No Drawing. Application July 2, 1956, Serial No. 595,077

3 Claims. (Cl. 260-401) This invention relates to novel compositions and to methods for producing them. In one of its more specific aspects the invention is directed to the methodsfor making and to novel derivatives of metal salts of polyamino acids, which I shall hereinafter term polyamino acid metal salts. Said polyamino acid metal salts" employed as starting materials in the practice of this invention have the following general formula:

FORMULA I v in which R is a hydrocarbon radical of at least 4 carbon atoms and for most purposes is 6-18 carbon atoms and may be aliphatic or aliphatic-aromatic; D is selected from the class consisting of CH2 and CONHRz; R2 is unsubstituted or hydroxy substituted aliphatic hydrocarbon radical of 2-4 carbon atoms, such as Cal-I4, CsHs, C3H5OH;. Y is selected from the class consisting of hydrogen, R7 and RCOOM; R5 is an aliphatic hydrocarbon group of 1-4 carbon atoms, such as CH2, C2H4, CaHe, C4H8 or an hydroxy substituted aliphatic hydrocarbon group of 2-4 carbon atoms, such as CHzCI-IOHCHz, or an aliphatic ether group of 3-4 carbon atoms containing a single ether linkage therein and otherwise being hydrocarbon or hydroxy substituted hydrocarbon; R7 is selected from the class consisting of CH3 and monovalent radicals otherwise defined as R2 such as C2H5, CsHv, CHzOH, C2H4OH, etc.; a is an integer in the range of 1-5; M is an alkali metal and preferably sodium or potassium.

Said polyamino acid metal salts may be produced in a number of different ways well known to the art. For example, RCOOH may be reacted with a polyamine NH2R2(NHR2)NH2 in the mole proportion of 1 to 1 and water of reaction is removed in the Well known manner to provide:

For example, a hydrocarbon chloride RCHzCl is reacted with a polyamine NHzRzNHa in the mole proportion of l to l and the hydrochloride of reaction is removed With caustic soda to produce:

RCHzNHRaNI-Ia For example a hydrocarbon chloride RCHzCl may be reacted with H(NHR2)NH2 in the mole proportion of 1 to 1 and the hydrochloride of reaction is removed with caustic soda to provide:

RCHz NHRa :cNHZ

Compounds of the last formula may be produced by reacting RNHz with ethylene oxide and ammonia.

Many polyamines are readily available in large commercial quantities. These amines are preferably employed in the pro ductionof my starting materials of this Patented Feb. 12, 1957 invention and have the following formulas and hereinafter known as reactants A, B, C, and D respectively:

These particular polyamines are generally produced by reacting ethylene oxide with ammonia. Polyamines containing additional ethyl amino groups can be obtained in the same manner. By employing propylene oxide instead of ethylene oxide homologues of the polyamines above set forth may be obtained, which contain propyl groups instead of the ethyl groups therein.

For example, glyceryl polyamines may be prepared by reacting 1 mole of epichlorhydrin "lee with 2 moles of aqueous ammonia in the well known manner to produce NHaCHzCHOHCHaNHaHCl which is treated with caustic soda to remove the HCl to provide reactant E.

NHzCHaCHOI-ICHaNHa which may be reacted with RCHzCl in equimolecular proportions to provide compounds:

which may be employed in the production of starting materials.

Said NHzCHzCHOHCI-IzNH-z may be reacted with NHzCHzCHOHCHzCl in the mole proportion of l to l and subsequently treated with caustic soda to remove the HCl to provide reactant F NHzCHzCHOHCHzNI-ICHzCHOHCHzNHa Said NHzCI-IzCHOHCHzNHz may be reacted with epichlorhydrin and ammonia and subsequently treated with caustic soda to obtain reactant G.

NH2CH2CHOHCH2NHCH2 CHOHCHzNHCHaCHOHCHaNHz For example, butyl polyamines may be obtained by reacting butyl diamine NH2C4H8NH2 with butyl dichloride in the mole proportion of 2-1 and in the presence of caustic soda to obtain reactant H.

with such methods being known to the art.

For example, 1 mole respectively of reactants B-E, G-H may be reacted with 1 mole of lauric acid C11H23COOH, capric acid CsHraCOOH, nonyl benzoic acid CsH19CsH4COOH until 1 mole of water of reaction has been formed and removed to provide compounds ln which C11H23CO, C9H19CO-, and C9H1sCsH4-CO respectively are substituted for a single hydrogen of only one of the terminal NH2 groups, such methods being well known to the art.

The starting materials of this invention may be produced by reacting a polyamine which is at least a diamine with RCH2 halogen and subsequently treated with caustic soda, or a polyamine which is at least a triamine with RCOOH to provide R-D-(i ]-Ra) .NH

which may be reacted with monohalocarboxylic acid together with caustic soda or potassium hydroxide. The monohalocarhoxylic acid generally used may be monochloracetic, monochlorlactic, monochlorpropionic, etc. so that R is CH2, C2H4, CsI-Is, Gil-Is, CHzCHOI-I, etc. In general the reaction is carried out by employing 1 mole of said compound and 1 or more moles of monohalocarboxylic acid and 2 moles of caustic soda or potassium hydroxide for each mole of monohalocarboxylic acid used. If the number of moles of monohalocarboxylic acid employed is less the number of hydrogens 0n the amine groups, apart from the H of the CCNI-I group if said group is present, then 1 or more of them if desired may be reacted with CHsCl, C2H5Cl, CsI-IvCl, ethylene chlorhydrin etc. then with caustic to provide radicals such as C2H5, CaHv, C2H4OH etc. for one or more of such hydrogens.

The following are given merely by way of illustrating in general methods well known to the art for producing examples of starting materials which may be employed in the practice of this invention.

. Examples A-H 1 mole of C11H23CH2NHC2H4NH2 is reacted with one mole of monochloracetic acid together with 2 moles of caustic soda to provide product A:

H r C1 H2a-CH NHCzH N CHz-COONa 1 mole of product A is reacted with 1 mole of monochlorlactic acid together with 2 moles of caustic soda to provide a mixture of product B and product 13-1 of the following formulas:

and

CHIOHOH-COONB O11Hq3CHz-NHC7H4-N OHr-CO ONa 1 mole of mixture of products B and B1 is reacted with 1 mole of monochlorpropionic acid together with 2 moles of caustic soda to provide products C and (3-1 which are the same as products B and B-1 respectively except that C2H4COONa is substituted for the hydrogens thereof attached directly to the nitrogens.

1 mole of product A is reacted with 2 moles respectively of methyl chloride and subsequently treated with caustic soda to remove the HCl of reaction to provide product D:

1 mole of product A is reacted with 2 moles of ethylene chlorhydrin and 2 moles of caustic soda to provide product E:

7 1 mole of product A is reacted 3 moles of monochloracetic acid together with 6 moles of caustic soda to provide product F.

Using the same type of reactants as those employed for the production of product A except that C9H19CH2 and C9H1cCeI-I4CH2 are respectively substituted for the radical C11Hzs-CHz to provide products G and H.

Examples I-CC 1 mole of C11H2s-CH2NHC2H4(NHC2H4)3NH2 is reacted with 1 mole of m'onochloracetic acid together with 2 moles of caustic soda to replace a hydrogen of the NHz with CHz-COONa to provide product I.

; tively of ethylene chlorhydrin and caustic soda to replace 1-4 of the hydrogens attached directly to the nitrogen atoms with C2H4OH to provide products TW.

1 mole of product K is reacted with 1-3 moles respectively of ethylene chlorhydrin and caustic soda to replace 1-3- of the hydrogen atoms attached directly to the nitrogen atoms with C2H4OH to provide products X--Z.

1 mole of product L is reacted with l-2 moles respectively of ethylene chlorhydrin and caustic soda to replace l-2 of the hydrogen atoms connected directly to the nitrogen atoms with C2H4OH to provide products AA and BB.

1 mole of product M is reacted with 1 mole of ethylene chlorhydrin and caustic soda to replace the single hydrogen connected directly to a nitrogen atom with -C2H4OH to provide product CC.

Examples DD-II 1 mole of C1iHaa-CONH-C2H4NHC2H4NH2 is reacted with 1 mole of monochloracetic acid together with 2 moles of caustic soda to provide product DD:

1 mole of product DD is reacted with 1-2 moles respectively of monochloracetic acid and 24 moles of caustic soda respectively to provide respective products EE and FF having the following respective formulas:

CH2-COONa and OHz-COONa 1 mole of product DD is reacted with 1-2 moles respectively of ethylene chlorhydrin and caustic soda to provide products 66 and HH respectively having the following respective formulas:

1 mole of product HH is reacted with 2 moles of monochloracetic acid and 2 moles of monochlorlactic acid respectively together with 4 moles of caustic soda respectively to provide products HH and II of the following respective formulas:

and 6 moles of caustic soda respectively to provide products J] and KK respectively:

Example LL 1 mole of produced by reacting 1 mole of C5HsCsH4-COOH with 1 mole of reactant G, is reacted with 1 mole of monochloracetic acid together with 2 moles of potassium hydroxide to provide product LL:

H l C 11 1-C5H -CONHCH CHOHCHg (NHCHzCHOHCHz)gN HE-COOK Examples MM-VV 1 mole of C11H23CONHC2H4(NHC2H4)aNHz is reacted with 1 mole of monochloracetic acid together with 2 moles of caustic soda, whereby a hydrogen of the NHz group is replaced by CHzCOONa which is product MM.

1 mole of product MM is reacted with 1-4 moles respectively of monochloracetic acid together with 28 moles of caustic soda to provide products NN, 00, PP, and QQ which are compounds the same as MM, except that 1-4 of the hydrogensattached to the nitrogens other than that of the CONHC2H4 group are replaced by CHzCOONa.

1 mole of product MM is reacted with 1-4 moles respectively of ethylene chlorhydrin and then treated with caustic soda, whereby 1-4 of the hydrogens thereof connected to such nitrogens other than that in the CONHC2H4 group is replaced by C2H4OH to provide products RR, SS, TT, and UU.

1 mole of product MM is reacted with a mixture of 2 moles of monochloracetic acid and 2 moles of ethylene chlorhydrin and then treated with 6 moles of caustic soda,

whereby two CHzCOONa groups and two C2H4OH groups replace the hydrogens attached to, the nitrogen groups other than that in the CONHC2H4 groups. The product is W.

The specific monocarboxylic acids, as well as the specific monohalo-monocarboxylic acids employed in certain examples, may be replaced by others as may be the various other reactants in the specific examples to provide a great number of other starting materials, which differ from those set forth in the examples heretofore set forth.

Prior to this invention, it was known that cationic surface active agents and anionic surface active agents when together in aqueous solution resulted in the production or formation of water insoluble compounds, and that adding an anionic surface active agent to an aqueous solution of another anionic surface active agent resulted in a mere physical combination of said agents and that no reaction would occur between them.

Said polyamino acid metal salts normally behave anionically in aqueous solutions having a pH above 7, and consequently it was expected that said polyamino acid metal salts when in aqueous solution together with anionic surface agents that they would be combined physically only and that no chemical reaction would occur therebetween. In the course of my experimentations, I have discovered that said polyamino acid metal salts could be reacted with certain anionic surface active agents at a pH above 7 to produce water-soluble reaction products. Not only did I make said discovery, but I further discovered that water solutions of such reaction products had viscosities greater than corresponding aqueous solutions of polyamino acid metal salts and also exhibited better foaming characteristics than did said polyamino acid metal salts in very low dilutions under extreme Water hardness conditions. Said reaction products are non-toxic and non-irritating to the human skin. They have been found eminently useful as general utility detergents, such as for car washing, dish washing, clothes washing, etc. Said polyamino acid metal salts as well as compounds of Formula II, hereinafter described and mere physical mixtures of said polyamino acid metal salts and compounds of Formula II when used as components of shampoos sometimes caused slight irritation or stinging of the eyes when such shampoos were used and water solutions thereof accidentally reached the eyes. I have further discovered that the reaction products of this invention caused practically no irritation or stinging of the eyes when so employed.

According to this invention, one or a combination of two or more of said polyamino acid metal salts of the general structural Formula I are reacted with one or a combination of two or more anionic surface active agents of the following general structural Formula II to provide novel, water-soluble compounds having the following general structural Formula III, and having high wetting, detergency and surface active properties and capable of providing voluminous and stablefoarns in aqueous solutions, and which aqueous solutions are substantially nonirritating to the skin and eyes of normal human beings.

[m-ooo -iu-x 0 wherein R3 is selected from the group consisting of (a) aliphatic and aliphatic-aromatic hydrocarbon radicals of 6-18 carbon atoms, with the aliphatic-aromatic hydrocarbon radicals each having an aliphatic radical of at least 6 carbon atoms; R4 is selected from the group consisting of (b) aliphatic hydrocarbon groups of 1-12 carbon atoms, (c) hydroxy substituted aliphatic hydrocarbon groups of l-l2 carbon atoms, (d) aliphatic ether groups, each of said groups having at least one ether oxygen linkage therein and otherwise being hydrocarbon of 2-12 carbon atoms, (2) hydroxy substituted aliphatic ether groups, each of said groups having at least one ether oxygen linkage therein, and otherwise being hydroxy substituted hydrocarbon of 2-12 carbon atoms, (f) aliphatic groups, each group containing aCONH-linkage therein and otherwise being hydrocarbon of 2-12 carbon atoms; X is a radical selected from the group consisting of S03 and 0503: M, R, D, R2, R5, Y, and a have heretofore been defined in Formula I; and b is zero to 5 and no greater than a; c is zero to 1; the sum of b and c is at least 1.

According to this invention, I react a compound of Formula I with a compound of Formula II to provide the novel and highly useful compounds of Formula III. In general, this reaction is carried out in a solution containing compounds I and II and to which a quantity of an acidic agent such as a strong mineral acid, as for example hydrochloric, sulphuric or its equivalent, has been added to lower the pH of the solution to a value of approximately 7 to approximately 9 and while maintaining the mass at a temperature between approximately 100-200" F. In this reaction under the aforesaid conditions, the compounds of Formula III are produced, said compounds having high water solubility in spite of the fact that the number of carbon atoms in R3 is 6 or more. Such compounds of Formula III have an unexpected extremely high water-solubility, while the corresponding salts of cationic compounds are water-insoluble. The resultant aqueous solution can be used directly as a surface active agent, wetting agent or detergent for the puiposes indicated for the polyamino acid metal salts. While the quantities of the compound of Formula I and compound of Formula II may be equimolecular for good yield of compounds of Formula III, I may employ an excess of either, and in general the mole ratio of a compound of Formula I to compound of Formula II may be 2 moles of the former to 1-10 moles of the latter depending upon the particular compound of Formula II employed.

One of the specific methods which I prefer to employ in carrying out an aspect of this invention is to first dissolve about 1 mole of a compound of Formula I in a quantity of water measuring about 1.5 times the weight of compound of Formula I used and then the pH thereof is adjusted to approximately 12-13 (measured electrically) by the addition of aqueous caustic soda if required so that when a compound of Formula II is added thereto, the pH of the solution of I and II will be at least and generally 105-11. The temperature of said solution is raised to l00200 F. and preferably in factory practice to approximately 140 F. Then about 1-5 moles of a compound of Formula II is dissolved in a quantity of water measuring by weight 1.5 times the quantity of compound of Formula II in a separate container and this solution is added to said first solution and the mass is maintained in said temperature range while being constantly stirred, and an acidic agent is added thereto to reduce the pH thereof to a value below 10 and in the range of approximately 7 to 9, and preferably of approximately 8.2 to approximately 8.7. At the end of the acidic agent addition, the stirring is continued and the temperature of the mass maintained for about 10-20 minutes after which the solution is allowed to cool and is a finished product.

The following are specific examples merely given by way of illustrating the invention and are not to be taken by way of limitation, all parts being given by weight unless otherwise specified.

Cir

Example 1 An aqueous solution of 310 parts of product A to 460 parts of water is heated to approximately F. and its pH (measured electrically) is adjusted by the addition of aqueous caustic soda to 12-13. While being constantly stirred and maintained at that temperature, there is added .a solution of 350 parts of:

in 525 parts of water. Then While stirring and the tempeerature is maintained, there is added thereto between about 30-40 parts of hydrochloric acid solution (32%), whereby the pH of the mass is lowered to a value in the range of 8.2 to 8.7. Stirring is continued and the temperature maintained for about 10 minutes more. The resultant product is a solution of the novel reaction prodnot, having the following formula:

Employ the same procedure and components as set forth in Example 1, except that only parts of Example 3 500 parts of product B in 750 parts of water. parts of:

CsHrz-COOCH2CHOH--CH2SOsNa in 920 parts of water.

FORDIULA OF NOVEL REACTION PRODUCT CHaCHOHCO 0N8 CnHn-CH2N C2H-N CaHi1C O O-- CH2 (CHOH)CH2S 0a OaHn-C O 0- 01120 HOE-CHz-S O3 OHzCOONa Example 4 510 parts of product C in 760 parts of water. parts of:

. CHaOH C1 H3 GO0OHriJCHg0SOa-Na HzOH in 750 parts of water.

FORMULA on NOVEL REACTION PRODUCT H/C2H4-COON8.

GnH23-OH1N N\ OHaCHOH-COONa CHz-CO ONa CHzOH Example 450 parts of product H in 700 parts of water. parts of:

CsHm-COO-CzHr-OSOa-Na in 1200 parts of water.

FORMULA OF NOVEL REACTION PRODUCT CHr-COONa om oooNa v OHr-OO ONu CoH1aCOO-C|H4-OSOI CrvHrn-C O O-GaHr-OS Os Example 6 425 parts of product I in 650 parts of water. parts of C11H23--COOC2H4CHOHOCH2-OS03N8.

in 2400 parts of water.

FORMULA OF NOVEL REACTION PRODUCT t CnHgr-CHa-NH- CgHgNH C:H4NH

Hr-OOONa mum-ooo-mmononocrnw or 3 FORMULA on NOVEL REACTION PRODUCT CnHgr-C ONH- C|H4N H C|H4-N/ H C Hr-C O O N a Example 10 675 parts of product H in 1,000 parts of water. parts of:

CIHIO CHaCHOH-COONa CH1-OOONB CxHaOCILCHOH-OOONQ.

Example 11 490 parts of product LL in 750 parts of water. parts of:

C11H23COOC2H4NHCOCH2SO3N&

in 1800 parts of water.

FORMULA OF NOVEL REACTION PRODUCT Example 7 850 parts of product N in 1300 parts of water. parts of:

C1OH21-COOC2H4NHCOCH2SO3=N&

in 750 parts of water.

FORMULA OF NOVEL REACTION PRODUCT C;nHa1-COO-C:H4NHCO CH2SOa CH2-COONO C Hu- C Hr-N C3H4N C:H4N CIHAN CzH4N H OHz-OOONa CHa-COOND.

CHg-GOONa CHg-COONit CHa-COONa Example 8 410 parts of product GG in 620 parts of water. parts of:

CsH13COO'C2H4OC2H4OC2H4-OSO3Na in 750 parts of water.

FORMULA OF NOVEL REACTION PRODUCT C2H4OH H CuHu-C ONH-CzH N C:H4-N

H CH1-COONB CsHis-CO O-GaHtO C2H4O C2H4-OSO:

Example 9 70 365 parts of product DD in 500 parts of water. 420 parts of:

in 650 parts of water.

CuHza-C O 0- CQHlNH C O CHr-S 0a Employing the same procedure as that set forth in Example 1, except that I mole proportion of products B-VV are respectively substituted for product A to provide other novel reaction products which are respectively the same as the formula of the novel reaction product of Example A except that there is substituted formulas of B-LL respectively for the formula of product A therein.

Following the same procedure as that set forth in Example 1 and employing 1 mol of any of said other starting materials of Formula I respectively, and 1 mol of any of the other specific compounds of Formula II, a great number of other novel reaction products whose formulas are that of Formula III may be produced; and in addition, the specific reactants employed may differ from those employed herein, within the definitions thereof, to provide a great number of other compounds of Formula III.

It is to be understood that instead of first adjusting the pH of the compound of Formula I to l2-13 before the addition of the compound of Formula II, any other method may be employed to obtain the condition where by the pH of the solution of I and II is at least 10 and preferably 10.5-11 before the addition of the acidic agent to lower the pH of the mass to approximately 7 to approximately 9. For example, I and II may be dissolved together and this solution may, by the addition of caustic soda when required, have its pH adjusted to at least 10, and then at -200 F. is ready for the addition of the acidic agent to lower its pH to approximately 7 to approximately 9. If desired, the required amount of acidic agent may be added either before or after the solution of pH of at least 10 is brought to a temperature in the range of 100-200 F.

Since certain changes in carrying out the aforesaid processes and certain modifications in the compositions "11 which embody the invention may be made'without departing from its scope, it is intended that all matter con tained in the description shall be interpreted as illustrative and not in a limiting sense.

It is also to be understood that when either S03 or 0803 is used in the specification or claims, it is meant to indicate either one or the other because of their obvious equivalency; it is also to be understood that the use of Na in the specification and claims is meant to indica-te any of the other alkali metals because of their obvious equivalency; it is also to be understood that the use of -CONH as employed herein is meant to indicate either it or -NHCO because of their obvious equivalency; and it is also to be understood that aliphatic as employed in the specification and claims in definition of R is meant to include straight and also branch chain aliphatic and cycloaliphatic.

It is also to be understood that the following claims are intended to cover all the generic and specific features of the invention herein described, and all statements of the scope of the invention which as a matter of language might be said to fall therebetween.

This application is a continuation-in-part of my copending application Ser. No. 575,300 filed April 2, 1956.

I claim:

1. A compound of the following formula:

[RaCOO-R4X c in which R is selected from the class consisting of allphatic and aliphatic-aromatic hydrocarbon radicals of 6-18 carbon atoms; D is selected from the class consisting of CH2 and CONHRz; R2 is selected from the class consisting of (a) aliphatic hydrocarbon radicals of 2-4 carbon atoms, (b) hydroxy substituted hydrocarbon radicals of 2-4 carbon atoms; Y is selected from the class consisting of (0) hydrogen, (0!) R7 and (e) Rs COOM; Rs

is selected from the class consisting of (f) hydrocarbon groups of 1-4 carbon atoms, (g) hydroxy substituted hydrocarbon groups of 2-4 carbon atoms, (11) ether groups, each of said groups having an ether-oxygen linkage therein and otherwise being hydrocarbon of 3-4 carbon atoms, (1) ether groups, each of said groups having an ether oxygen linkage therein and otherwise being hydroiry substituted hydrocarbon of 3-4 carbon atoms; R7 is selected from the group consisting of CH3 and radicals monovalent otherwise defined in R2; 0 is 1-5; b is zero to 5 and no greater than a; c is zero to l; the sum of b and c is at least 1; R3 is selected from the group consisting of (j) aliphatic and aliphatic-aromatic hydrocarbon radicals of 6-18 carbon atoms, with the latter having an aliphatic hydrocarbon radical of at least 6 carbon atoms; R4 is selected from the group consisting of (k) aliphatic hydrocarbon and hydroxy substituted hydrocarbon groups of l-l2 carbon atoms, (l) aliphatic ether groups, each of said groups having at least one ether oxygen linkage therein and otherwise being hydrocarbon of 2-12 carbon atoms, (in) aliphatic ether groups, each of said groups having at least one ether oxygen linkage therein and otherwise being hydroxy substituted hydrocarbon of 2-12 carbon atoms, (n) aliphatic groups, each of said groups containing a CONH- linkage therein and otherwise being hydrocarbon of 2-12 carbon atoms; X is selected from the group consisting of S03 and 0803; and M is an alkali metal.

2. A compound defined in claim 1, and with R, D, R2, R3 and R5 being hydrocarbon-as therein defined.

3; A compound defined in claim 1, and with D being CONH and R, R2, R3 and R5 being hydrocarbon as therein defined.

References Cited in the file of this patent UNITED STATES PATENTS Schocller et al. Dec. 28, 1937 Isbell Nov. 25, 1952 OTHER REFERENCES Freese et 211.: American Perfumer, Shampoo Uses, March 1956, pages 37-40. 

1. A COMPOUND OF THE FOLLOWING FORMULA: 